U.S. patent number 7,091,297 [Application Number 10/683,167] was granted by the patent office on 2006-08-15 for shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments.
This patent grant is currently assigned to The University of Connecticut. Invention is credited to Qing Ge, Changdeng Liu, Patrick T. Mather.
United States Patent |
7,091,297 |
Mather , et al. |
August 15, 2006 |
**Please see images for:
( Certificate of Correction ) ** |
Shape memory polymers based on semicrystalline thermoplastic
polyurethanes bearing nanostructured hard segments
Abstract
Thermoplastic polyurethanes having an alternating sequence of
hard and soft segments in which a nanostructured polyhedral
oligomeric silsesquioxane diol is used as a chain extender to form
a crystalline hard segment constituting SMPs. The polyurethanes are
formed by reacting a polyol, a chain extender dihydroxyl-terminated
POSS and a diisocyanate. The polyurethanes have multiple
applications including for example, implants for human health care,
drug delivery matrices, superabsorbant hydrogels, coatings,
adhesives, temperature and moisture sensors, etc.
Inventors: |
Mather; Patrick T. (Storrs,
CT), Ge; Qing (Coventry, CT), Liu; Changdeng (Storrs,
CT) |
Assignee: |
The University of Connecticut
(Farmington, CT)
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Family
ID: |
32097153 |
Appl.
No.: |
10/683,167 |
Filed: |
October 10, 2003 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20040116641 A1 |
Jun 17, 2004 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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60488590 |
Jul 18, 2003 |
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60488323 |
Jul 18, 2003 |
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60466401 |
Apr 29, 2003 |
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60419506 |
Oct 18, 2002 |
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60418023 |
Oct 11, 2002 |
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Current U.S.
Class: |
528/28; 524/434;
524/442; 524/445; 525/424; 528/73; 528/74; 524/444; 524/437;
524/433; 524/428; 524/424; 524/404 |
Current CPC
Class: |
A61M
27/008 (20130101); C08J 3/005 (20130101); C08L
65/00 (20130101); C08G 18/4833 (20130101); C08G
18/718 (20130101); C08G 18/3893 (20130101); A61F
2/88 (20130101); C08G 18/61 (20130101); A61F
2/958 (20130101); C08G 65/336 (20130101); A61L
31/14 (20130101); C08L 71/02 (20130101); C08G
61/08 (20130101); C08L 71/02 (20130101); C08L
83/00 (20130101); C08L 2205/05 (20130101); A61F
2002/8483 (20130101); A61F 2220/0016 (20130101); A61F
2250/0037 (20130101); C08G 2230/00 (20130101) |
Current International
Class: |
C08G
18/32 (20060101); C08G 18/38 (20060101); C08G
18/40 (20060101); C08G 18/64 (20060101); C08G
18/76 (20060101) |
Field of
Search: |
;524/404,424,428,433,434,437,442,444,445 ;525/424
;528/28,73,74 |
References Cited
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WO |
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WO 2005/009523 |
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Feb 2005 |
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WO |
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WO 2005/070988 |
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Aug 2005 |
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WO |
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Primary Examiner: Sergent; Rabon
Attorney, Agent or Firm: Cantor Colburn LLP
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the priority of Provisional Applications
Ser. Nos. 60/418,023 filed Oct. 11, 2002, 60/466,40 1 filed Apr.
29, 2003; Ser. No. 60/419,506 filed Oct. 18, 2002; 60/488,590 filed
Jul. 18, 2003 and 60/488,323 filed Jul. 18, 2003, each of which is
incorporated herein in their entirety by reference thereto. Both
application Ser. No. 10/425,451 filed Apr. 29, 2003 which claims
priority from provisional application Ser. No. 60/377,544 and the
claimed provisional applications are also incorporated herein by
reference.
Claims
The invention claimed is:
1. A method for making a thermoplastic polyurethane shape memory
polymer comprising reacting in one step (A) a polyol, (B) a
polyhedral oligosilsesquioxane diol, and (C) a diisocyanate;
wherein the shape memory polymer exhibits a thermal triggering
temperature of 30.degree. C. to 60.degree. C.
2. The method of claim 1 wherein the polyhedral oligosilsesquioxane
diol is a member selected from the group consisting of
2-ethyl-2-[3-[[(heptacyclopentylpentacyclo-[9.5.1.1.sup.3,9.1.sup.5,15.1.-
sup.7,13]octasiloxanyl)oxy[dimethylsilyl]-propoxy]methyl]-1,3-propanediol,
2-ethyl-2-[3-[[(heptacyclohexylpentacyclo-]9.5.1.1.sup.3,9.1.sup.5,15.1.s-
up.7,13]octasiloxanyl)oxy[dimethylsilyl]-propoxy]methyl]-1,3-propanediol,
2-ethyl-2-[3-[[(heptaisobutylpentacyclo-[9.5.1.1.sup.3,9.1.sup.7,13]octas-
iloxanyl)oxy]dimethylsilyl]-propoxy]methyl]-1,3-propanediol,
1-(2-trans-cyclohexanediol)ethyl-3,5,7,9,11,13,15-cyclohexanepentacyclo-[-
9.5.1.1.sup.3,9.1.sup.5,15.1.sup.7,13]octasiloxane, and
1-(2-trans-cyclohexanediol)ethyl-3,5,7,9,11,13,15-isobutylpentacyclo-[9.5-
.1.1.sup.3,9.1.sup.5,15..sup.7,13]octasiloxane.
3. The method of claim 1 wherein the diisocyanate is a member
selected from the group consisting of 4,4'-diphenyl methylene
diisocyanate (MDI), toluene-2,4-diisocyanate (TDI),
toluene-2,6diisocyanate, hexamethylene-1,6-diisocyanate (HDI),
isophorone diisacyanate (IPDI), and hydrogenated
4,4'-diphenylmethane diisocyanute (H12MDI).
4. The method of claim 1 wherein the diisocyanate is 4,4'-diphenyl
methylene diisocyanate.
5. A thermoplastic polyurethane shape memory polymer according to
claim 1 containing a filler which is a member selected from the
group consisting of boron nitride, silica, titanium dioxide,
montmorillonite, clay, staple, aluminum nitride, barium
subcarbonate, and bismuth subcarbonate.
6. The method of claim 1, wherein the thermoplastic polyurethane
shape memory polymer exhibits a thermal triggering temperature of
37.degree. C. to 50.degree. C.
7. A method for making a thermoplastic polyurethane shape memory
polymer comprising reacting in one step (A) a polyol, (B)
polyhedral oligosilsesquioxane diol, and (C) a diisocyanate,
wherein the polyol is a member selected from the group consisting
of polyethylene glycol (PEG), polycaprolactone (PCL) diol,
polycyclooctene diol, polynorbornene diol and polymethacrylate
copolymer.
8. A method for making a thermoplastic polyurethane shape memory
polymer comprising reacting in one step (A) a polyol, (B) a
polyhedral oligosilsesquioxane diol, and (C) a diisocyanate,
wherein the polyol is a member selected from the group consisting
of polyethylene glycol, polycaprolactone diol, and polycyclooctene
diol, and is semicrystalline.
9. A method for making a thermoplastic polyurethane shape memory
polymer comprising reacting in one step (A) a polyol, (B) a
polyhedral oligosilsesquioxane diol, and (C) diisocyanate, wherein
the polyol is an amorphous diol having a Tg in the range of 20
80.degree. C., and is a member selected from the group consisting
of polynorbornene diol and polymethacrylate copolymer diol.
10. A method for making a thermoplastic polyurethane shape memory
polymer comprising reacting in one step (A) a polyol, (B) a
polyhedral oligosilsesquioxane diol, and (C) a diisocyanate,
wherein the polyol is a member selected from the group consisting
of polyethylene glycol, polycaprolactone diol, and polycyclooctene
diol; wherein the polyhedral oligosilsesquioxane diol is a member
selected from the group consisting of
2-ethyl-2-[3-[[(heptacyclopentylpentacyclo-[9.5.1.1.sup.3,9.1.sup.5,15-
.1.sup.7,13]octasiloxanyl)oxy[dimethylsilyl]-propoxy]methyl]-1,3-propanedi-
ol,
2-ethyl-2-[3-[[(heptacyclohexylpentacyclo-]9.5.1.1.sup.3,9.1.sup.5,15.-
1.sup.7,13]octasiloxanyl)oxy]dimethylsilyl]-propoxy]methyl]-1,3-propanedio-
l,
2-ethyl-2-[3-[[(heptaisobutylpentacyclo-[9.5.1.1.sup.3,9.1.sup.7,13]oct-
asiloxanyl)oxy]dimethylsilyl]-propoxy]methyl]-1,3-propanediol,
1-(2-trans-cyclohexanediol)ethyl-3,5,7,9,11,13,15-cyclohexanepentacyclo-[-
9.5.1.1.sup.3,9.1.sup.5,15.1.sup.7,13]octasiloxane, and
1-(2-trans-cyclohexanediol)ethyl-3,5,7,9,11,13,15-isobutylpentacyclo-[9.5-
.1.1.sup.3,9.1.sup.5,15..sup.7,13]octasiloxane; and wherein the
diisocyanate is 4,4'-diphenyl methylene diisocyanate.
11. The method of claim 10 wherein said reaction is carried out in
presence of dibutyltin dilaurate as catalyst.
12. A method for making a thermoplastic polyurethane shape memory
polymer comprising reacting in one step (A) a polyol, (B) a
polyhedral oligosilsesquioxane diol, and (C) a diisocyanate,
wherein the polyol is polyethylene glycol, wherein the polyhedral
oligosilsesquioxane is
1-(2-trans-cyclohexanediol)ethyl-3,5,7,9,11,13,15-isobutylpentacyclo-[9.5-
.1.1.sup.3,9.1.sup.5,15.1.sup.7,13]octasiloxane, and wherein the
diisocyanate is 4,4'-diphenyl methylene diisocyanate.
13. A method for making a thermoplastic polyurethane shape memory
polymer comprising reacting in one step (A) a polyol, (B) a
polyhedral oligosilsesquioxane diol, and (C) a diisocyanate,
wherein the polyol is polycyclooctene diol, wherein the polyhedral
oligosilsesquioxane diol is
2-ethyl-2-[3-[[(heptaisobutylpentacyolo-[9.5.1.1.sup.3,9.1.sup.5,15.1.sup-
.7,13]octasiloxanyl)oxy]dimethytsilyl]-propoxy]methyl]-1,3-propanediol,
and wherein the diisocyanate is 4,4'-diphenyl methylene
diisocyanate.
14. A thermoplastic polyurethane shape memory polymer prepared by
the method of claim 10.
15. A thermoplastic polyurethane shape memory polymer prepared by
the method of claim 11.
16. A thermoplastic polyurethane shape memory polymer prepared by
the method of claim 11.
17. A thermoplastic polyurethane shape memory polymer prepared by
the method of claim 13.
18. A thermoplastic polyurethane shape memory polymer prepared by a
method comprising reacting in one step (A) a polyol, (B) a
polyhedral oligosilsesquioxane diol, and (C) a diisocyanate,
wherein the thermoplastic polyurethane shape memory polymer
exhibits a thermal triggering temperature of 30 to 60.degree.
C.
19. The thermoplastic polyurethane shape memory polymer of claim
18, wherein the thermoplastic shape memory polymer exhibits a
thermal triggering temperature of 37.degree. C. to 50.degree.
C.
20. A thermoplastic polyurethane shape memory polymer having the
formula ##STR00005## wherein R is isobutyl, wherein the ratio of
x:y is 1 to 20, the polyol degree of polymerization is
1<n<1000 and the total degree of polymerization,
2<m<100.
Description
TECHNICAL FIELD
The instant disclosure relates to shape memory polymers and more
particularly thermoplastic polyurethanes with an alternating
sequence of hard and soft segments in which a nanostructured
polyhedral oligomeric silsesquioxane diol is used as a chain
extender to form a crystalline hard segment and also relates to
methods for the preparation of these thermoplastic polyurethanes
and to applications thereof.
BACKGROUND OF THE DISCLOSURE
Shape memory materials feature an ability to transform shape from a
temporary, frozen, shape to a permanent shape when triggered by an
environmental stimulus, such as heat, light, or vapor. Used
creatively, these phenomena can be exploited for a wide range of
applications. While both shape memory alloys (SMAs) and shape
memory polymers (SMPs) show similar thermo-stimulated shape memory
properties, their mechanisms of action are quite distinct.
Advantages of SMAs include rapid strain recovery (within 1 second),
the potential training for two-way reversible memory, and an
apparent superelasticity due within the austentite phase at low
temperature. In contrast, polymers intrinsically exhibit shape
memory effects derived from their highly coiled constituent chains
that are collectively extensible via mechanical work and this
energy may be stored indefinitely, known as "shape fixing," by
cooling below T.sub.g or T.sub.m. The polymeric samples can later
perform mechanical work and return to a stress-free state when
heated above the critical temperature, mobilizing the frozen chains
to regain the entropy of their coiled state. In comparison to SMAs,
thermally stimulated SMPs have the advantages of: (i) large
recoverable deformations in excess of several hundred percent
strain; (ii) facile tuning of transition temperatures through
variation of the polymer chemistry; and (iii) processing ease at
low cost.
Thermally stimulated SMPs with different thermomechanical
properties to function in various applications, for example as
medical devices and mechanical actuators have previously been
synthesized and characterized. The materials span a range of room
temperature moduli, from rigid glassy materials having storage
moduli of several GPa to compliant rubbers with moduli as low as
tens of MPa. Moreover, the retracting (rubbery) moduli have been
adjusted over the range 0.5<E<10 MPa, as prescribed by the
end application. One such example is chemically crosslinked
polycyclooctene (PCO), a stiff semicrystalline rubber that is
elastically deformed above T.sub.m to a temporary shape that is
fixed by crystallization. Fast and complete recovery of gross
deformations is achieved by immersion in hot water. These SMPs have
been described in Provisional Patent Application Ser. No.
60/419,506 filed Oct. 18, 2002 entitled Chemically Crosslinked
Polycyclooctene, the entirety of which is incorporated herein by
reference. In Provisional Patent Application Ser. No. 60/377,544
filed May 2, 2002 entitled Castable Shape Memory Polymers, the
entirety of which is incorporated herein by reference, stiffer SMPs
offering tunable critical temperatures and rubber modulus using a
thermosetting random copolymer made of two vinyl monomers that
yield controlled T.sub.g and casting-type processing are described.
Such copolymers were crosslinked with a difunctional vinyl monomer
(crosslinker), the concentration of crosslinker controlling the
rubber modulus and thus the work potential during recovery. Besides
their shape memory effects, these materials are also castable
allowing for processing more complex shapes. In addition, they are
optically transparent making them useful for additional
applications.
The use of chemical crosslinking in both of these cases limits the
types of processing possible and forever sets the equilibrium shape
at the point of network formation. Therefore, miscible blends of a
semicrystalline polymer with amorphous polymers have also been
intensively investigated due to their attractive crystalline
properties and mechanical properties. For those blends that are
miscible at the molecular level, a single glass transition results,
without broadening, an aspect important to shape memory.
Additionally, in such miscible blends the equilibrium crystallinity
(which controls the plateau modulus between T.sub.g and T.sub.m
where shape fixing is performed) also changes dramatically and
systematically with the blend compositions. It provides a simple
route to alternative shape memory plastics; i.e. SMPs with
relatively high modulus in the fixed state at room temperature,
having a tunable and sharp transition, and the permanent shape can
be remolded repeatedly above certain melting temperatures. These
SMP blends have been described in Provisional Patent Application
Ser. No. 60/466,401 filed Apr. 29, 2003 entitled Blends of
Amorphous and Semicrystalline Polymers with Shape Memory
Properties, the entirety of which is incorporated herein by
reference.
Microphase-separated semicrystalline thermoplastic polymers with
two sharp melting transitions T.sub.m2>T.sub.m1>room
temperature, where the difference of the two melting points is at
least 20.degree. C., are also good candidates for shape memory
offering the advantage of melt processing above T.sub.m2, and
repeated resetting of the equilibrium shape by relaxing stress in
the fluid state. Representative past examples of such polymers in
this class of SMP are conventional polyurethanes whose soft domains
are glassy or semicrystalline with low melting point (but higher
than T.sub.crit) and whose hard domains feature a higher melting
point only exceeded during processing.
OBJECTS OF THE DISCLOSURE
It is an object of the present disclosure to provide shape memory
polymers comprising hybrid polyurethanes.
It is another object of the disclosure to provide shape memory
polymers having medium and tunable modulus in the fixed state at
room temperature, having a tunable and sharp transition, whose
permanent shape can be repeatedly remolded above a certain melting
temperature.
It is another object of the disclosure to provide hybrid
polyurethane SMPs evidencing sharp and tunable transition
temperatures, adjustable stiffness above their transition
temperatures and thermal processability above the melting point of
the POSS domains.
It is yet another object of the disclosure to provide hybrid
polyurethane SMPs which possess excellent shape recovery effect at
the recovery temperature and wherein the retracting force is
adjustable according to the composition of the POSS.
Still a further object of the disclosure is to provide hybrid
polyurethanes that are biocompatible and can be used as medical
devices and implants.
Yet another object of the disclosure is a method for synthesizing
such hybrid polyurethanes.
SUMMARY
Broadly the disclosure provides a method for producing hybrid
polyurethane SMPs by reacting (A) a polyol, (B) a chain extender
dihydroxyl-terminated POSS and (C) a dilisocyanate, wherein POSS
stands for a polyhedral silsesquioxane diol. The polyol (A) can be
polyethylene glycol (PEG), polycaprolactone (PCL) diol,
polycyclooctene diol, trans-1,4 butadiene, transisoprene,
polynorbornene diol and polymethacrylate copolymer. The chain
extender (B) can be TMP cyclopentyldiol-POSS
(2-ethyl-2-[3-[[(heptacyclopentylpentacyclo-[9.5.1.1.sup.3,9.1.sup.5,15.1-
.sup.7,13]octasiloxanyl)oxy]dimethylsilyl]-propoxy]methyl]-1,3-propanediol-
, Chemical Abstracts Registry No. 268747-51-9), TMP
cyclohexyldiol-POSS
(2-ethyl-2-[3-[[(heptacyclohexylpentacyclo-[9.5.1.1.sup.3,9.1.sup.5,15.1.-
sup.7,13]octasiloxanyl)oxy]dimethylsilyl]-propoxy]methyl]-1,3-propanediol)-
, TMP isobutyldiol-POSS
(2-ethyl-2-[3-[[(heptaisobutylpentacyclo-[9.5.1.1.sup.3,9.1.sup.5,15.1.su-
p.7,13]octasiloxanyl)oxy]dimethysilyl]-propoxy
]methyl]-1,3-prapanediol), trans-cyclohexanediolcyclohexane-POSS
(1-(2-trans-cyclohexanediol)ethyl-3,5,7,9,11,13,15-oyclohexanepentacyclo--
[9.5.1.1.sup.3,9.1.sup.5,15.1.sup.7,13]octasiloxane), or
transcyclohexanediolisobutyl-POSS
(1-(2-trans-cyclohexanediol)ethyl-3,5,7,9,11,13,15-isobutylpentacyclo-[9.-
5.1.1.sup.3,9.1.sup.5,15.1.sup.7,13])octasiloxane, Chemical
Abstracts Registry No. 480439-48-3). And the diisocyanate (C) can
be selected from a large number of diisocyanates and is preferably
4,4' diphenyl methylene dilsocyanate (MDI). Other diisocyanates (C)
that are suitable for use in the synthesis of hybrid polyurethane
SMPs include: toluene-2,4-diisocyanate (TDI),
toluene-2,6diisocyanate, hexamethylene-1,6-diisocyanste (HDI),
isophorone diisocyanate (IPDI), and hydrogenated
4,4'-diphenylmethane diisocyanate (H12MDI).
The polyol can be semicrystalline and preferably selected from
polyethylene glycol (PEG), polycaprolactone (PCL) diol,
polycyclooctene diol, trans-1,4 butadiene, transisoprene or it can
be amorphous in which case it can be polynorbornene diol and/or
polymethacrylate copolymer.
The method for producing hybrid polyurethane SMPs and the novel
hybrid polyurethanes prepared thereby are illustrated by the
following non-limiting reaction schemes.
##STR00001##
This scheme shows an example of synthesis of TPU using polyethylene
glycol as polyol, trans-cyclohexanediolisbutyl-POSS as chain
extender to react with 4,4' diphenyl methylene diisocyanate in
toluene.
##STR00002## This scheme shows an example of synthesis of TPU using
polycaprolactone diol as polyol, TMP Isobutyldiol-POSS as chain
extender to react with 4,4' diphenyl methylene diisocyanate.
##STR00003## This scheme shows an example of synthesis of TPU using
polycyclooctene diol as polyol, TMP Isobutyldiol-POSS as chain
extender to react with 4,4' diphenyl methylene diisocyanate.
A general formula for the POSS-based TPUs incorporating PEG diol,
prepared according to Scheme 1, follows. The polymers allow
systematic variation in the ratio of X/Y (1 to 20), the polyol
degree of polymerization (1<n<1000), and the total degree of
polymerization, 2<m<100.
##STR00004##
The instant hybrid polyurethanes demonstrate sharp and tunable
transition temperatures, adjustable stiffness above their
transition temperatures, and thermal processibilty above the
melting point of the POSS domains. The hybrid polyurethanes also
show excellent shape recovery effect at the recovery temperature
and a retracting force which is adjustable according to the
composition of the POSS. They also posses a unique property that is
different from the other shape memory polymers in that the current
disclosure (in the PEG embodiment) can be triggered to recover by
moisture (liquid or vapor) in addition to heating. For the thermal
triggering mechanism, the range 30.degree. C. to 60.degree. C.
according to the ratio of the components used and (importantly)
thermal annealing to achieve steady-state (equilibrium)
crystallinity is important. The recovery can be finished within
seconds when heated 20.degree. C. above the transition temperature.
The additional advantages of the materials include that the
materials are rigid at room temperature, the polymers generally are
biocompatible and in some cases biodegradable and can be used as
medical devices and implants. The products also can be dyed to any
color or rendered radio-opaque for d-ray radiography according to
application requirements.
Any of the hybrid polyurethane polymers mentioned above may be
filled with, for example, nanoparticles of boron nitride, silica,
titanium dioxide, montmorillonite, clay, Kevlar, staple, aluminum
nitride, barium and bismuth subcarbonate. Clay and silica can be
used to, for example, increase the modulus of the plastic.
Dispersing agents and/or compatibilizing agents may be used, for
example, to improve the blending of polymers and the blending of
polymers with fillers. Dispersing agents and/or compatibilizing
agents include, for example, ACRAWAX.RTM. (ethylene
bis-stearamide), polyurethanes and ELVALOY.RTM. (acrylic
functionalized polyethylene). The polymers can be cross-linked by
application of radiation such as e-beam, UV, gamma, x-ray radiation
or by heat-activated chemical crosslinking techniques. Radiation
techniques provide the advantage that the polymer typically does
not have to be substantially heated to achieve crosslinking. For
e-beam radiation, an exposure of about 200 300, e.g. 250 kilograys,
typically provides sufficient crosslinking.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates graphically the DMA plots of the TMP POSS based
thermoplastic polyurethane (TPU) with mole ratio of PEG: POSS as
1:6, 1:4 respectively;
FIG. 2 illustrates graphically the DSC results of TMP POSS based
TPU with different PEG:POSS mole ratios;
FIG. 3 illustrates the equipment as used for measuring
stress-strain; and
FIG. 4 illustrates graphically the stress-strain plot of the TMP
POSS based TPU (PEG:POSS=1.6).
DETAILED DESCRIPTION
Thermoplastic polyurethanes with different compositions were
synthesized by one-step condensation polymerization using the
scheme shown above. Toluene was used as solvent and dibutyltin
dilaurate was used as catalyst. The reaction was kept at 90.degree.
C. under the nitrogen for 2 hours and then cooled down to room
temperature and precipitated into hexane. The product was dried
thoroughly and dissolved in toluene to make a 10 wt % solution for
casting films. The molecular weights and molecular weight
distributions of this series of samples obtained from size
exclusion chromatography are summarized in Table 1.
TABLE-US-00001 TABLE 1 Molecular weights and molecular weight
distributions of POSS-based polyurethanes having polyol (PEG) block
length of 10000 g/mol Sample M.sub.n (g/mol) M.sub.w/M.sub.n
PEG:POSS = 1:3 47,400 1.42 PEG:POSS = 1:4 48,800 1.44 PEG:POSS =
1:6 54,000 1.54 PEG:POSS = 1:8 49,200 1.30
Samples of polyurethanes with different compositions were
characterized by differential scanning calorimetry (TA Instruments
DSC2920). All of the samples were characterized under the same
conditions: two scans were performed for each sample with heating
and cooling rates of 10.degree. C./min (FIG. 2). It was observed
that this series of polyurethanes exhibit two melting points, one
in the range 45<T.sub.m1<50.degree. C. corresponding to the
melting temperature of PEG "soft" block. The other melting
transition appears in the range 110<T.sub.m2<130.degree. C.,
which corresponds to the melting of a POSS-reinforced hard segment
phase. The melting temperature of the soft segment is observed to
shift to lower values with a broadening of the melting peak while
the melting temperature of the hard segment is observed to shift to
higher values with a sharpening of the melting peak when the mole
ratio of polyol:chain extender decreases. This result can be
explained in that as the PEG:POSS ratio decreases, the resulting
block copolymer will have less overall PEG content, which will
directly affect the size and perfection of the crystallization of
PEG blocks. Therefore, the melting temperature moves to lower
values and the peak is broadened. On the contrary, the content of
POSS will increase in the block copolymers, which provides for more
clear aggregation of hard segments to form larger and more perfect
crystals. Therefore, the melting temperature of hard segment moves
to higher values while the peak is sharpened (FIG. 2).
The dried films of the formed polyurethanes were cut into thin
strips for tests of temporary shape fixing and subsequent recovery,
or shape memory. For example, a sample was first heated on the hot
stage to 65.degree. C., which is well above the first transition
temperature but low enough to avoid melting of the elastic network
of the POSS-rich phase. It was then stretched to a certain degree
of elongation and cooled down to the room temperature. The deformed
shape was fixed at room temperature. Finally, the deformed sample
was heated up again on hot plate to 65.degree. C. and it was
observed that the sample restored to its original length completely
and within seconds. A similar phenomenon was observed when water
was used as a stimulus for the shape recovery except that the
sample secondarily swelled to form a tough hydrogel.
The hybrid polyurethanes of the disclosure can be used for the
following applications. a. Stents, patches and other implants for
human health care b. Surgical tools requiring adjustable shape but
high stiffness. c. Arbitrarily shape-adjustable structural
implements, including personal care items (dinnerware, brushes,
etc.) and hardware tool handles. d. Self healing plastics e.
Medical devices (a dented panel is repaired by heating or
plasticizing with solvent) f. Drug delivery matrices g.
High-strength thermoplastic (non-crosslinked) superabsorbant
hydrogels h. Aqueous Theological modifiers for paints, detergents
and personal care products i. Impression material for molding,
duplication, rapid prototyping, dentistry, and figure-printing. j.
Toys k. Reversible Embossing for information storage l. Temperature
and moisture sensors m. Safety valve n. Heat shrink tapes or seals
o. Heat controlled Couplings and fasteners p. Large strain, large
force actuators q. Coatings, adhesives r. Textiles, clothing
The shape memory polymers of the disclosure are particularly
suitable as biomaterials because of their low thromogenicity, high
biocompatibility, as well as unique mechanical properties. In
accordance with the disclosure the shape memory polyurethanes were
formulated such that the melting temperature of one segment falls
within a useful temperature range for biomedical application:
37.degree. C. 50.degree. C.
The present disclosure provides an advantageous shape memory
polymer that includes thermoplastic polyurethane shape memory
polymers formed by reacting in one step a polyol, a POSS chain
extender and a diisocyanate, having medium and tunable modulus in
the fixed state at room temperature having a tunable sharp
transition, whose permanent shape can be repeatedly remolded above
a certain melting temperature.
Although the polymers and processing methodologies of the present
disclosure have been described with reference to specific exemplary
embodiments thereof, the present disclosure is not to be limited to
such exemplary embodiments. Rather, as will be readily apparent to
persons skilled in the art, the teachings of the present disclosure
are susceptible to many implementations and/or applications,
without departing from either the spirit or the scope of the
present disclosure. Indeed, modifications and/or changes in the
selection of specific polymers, polymer ratios, processing
conditions, and end-use applications are contemplated hereby, and
such modifications and/or changes are encompassed within the scope
of the present invention as set forth in the claims which
follow.
* * * * *